N-(phenyl or benzyl)-n,n&#39;-bis-(1-amino-2,2,2-trichloro)-ethyl)alkyleniamines

ABSTRACT

Compounds of the formula   WHEREIN R1 is hydrogen, alkyl of one to four carbon atoms or trichloromethyl, R2 is phenyl, benzyl, chlorophenyl, dichlorophenyl, chlorobenzyl, dichlorobenzyl, bromophenyl or dibromophenyl, R3 is hydrogen, phenyl, benzyl or dichlorophenyl, bromophenyl or dibromophenyl, and N IS 1, 2 OR 3; THE COMPOUNDS ARE USEFUL AS FUNGICIDES.

United States Patent n91 0st at al.

[54] N-(PHENYL OR BENZYL)-N,N'-BlS-(l- AMlNO-2,2,2-TRICHLORO)-ETHYL)ALKYLENIAMINES [75] Inventors: Walter 0st, Klaus Thomas, DietrichJerchel, all of Ingelheim/Rhine;

Karl-Richard Appel, Biberach- Rissegg, all of Germany [73] Assignee: C.H. Boehringer Sohn, Ingelheim/ Rhine, Germany I [22] Filed: Marc iii5 ifi [21] Appl. No.: 128,168

Related U.S. Apnlication Data [63] Continuation-impart of Ser. No.793,187, Jan. 22,

l969, Pat. No. 3,595,916.

[52] U.S. Cl ..260/S62 P [5 l] Int. Cl ..C07c 103/30 [58] Field ofSearch ..260/562 [56] References Cited UNITED STATES PATENTS 3,520,9277/1970 Malz et al ..260/562 m1 3,716,587 51 Feb. 13,1973

Primary Examinerl-larry l. Moatz Attorney-Hammond 8L Littell 57 ABSTRACTCompounds of the formula wherein R is hydrogen, alkyl of one to fourcarbon atoms or trichloromethyl,

R, is phenyl, benzyl, chlorophenyl, dichlorophenyl, chlorobenzyl,dichlorobenzyl, bromophenyl or dibromophenyl,

R is hydrogen, phenyl,, benzyl or dichlorophenyl, bromophenyl ordibromophenyl, and

n is l, 2 or 3;

the compounds are useful as fungicides.

20 Claims, No Drawings N-(PHENYL R BENZYL)-N,N'-BlS-(l-AMINO-2,2,Z-TRICl-lLORO)-ETHYL)ALKYLENIAMINES This is a continuation-in-partof copending applica tion Ser. No. 793,187, filed Jan. 22, 1969, now US.Pat. No. 3,595,916.

This invention relates to novel N-(phenyl or benzyl)- N,N'-bis-[(l-amido-2,2,2-trichloro)-ethyl]-alkylenediamines, as well as to a methodof preparing these compounds.

R, is hydrogen, alkyl of one to four carbon atoms or trichloromethyl,

R is phenyl, benzyl, chlorophenyl, dichlorophenyl, chlorobenzyl,dichlorobenzyl, bromophenyl or dibromophenyl,

R is hydrogen, phenyl, benzyl or dichlorophenyl, bromophenyl ordibromophenyl, and

n is l, 2 or 3.

A compound of the formula I may be prepared by methods involving wellknown chemical principles, among which the following has proved to beparticularly convenient and efficient:

By reacting a compound of the formula wherein R has the same meanings asin formula I and X is a substituent which may easily be split off in theform of an anion, such as chlorine, bromine, arylsulfonyloxy,alkylsulfonyloxy, aryloxy, trifluoroacetoxy or arylcarbonyl-oxy, with analkylenediamine of the formula wherein R R and n have the same meaningsas in formula I, pursuant to the reaction formula The reaction ispreferably carried out in the presence of an inert organic solvent, suchas tetrahydro-furan, dioxane, toluene, acetone or a chlorinatedhydrocarbon, at a temperature between about 20 and +l00 C., preferablybetween +20 and +40 C.

When X in formula ll is chlorine or bromine, it is advantageous to addto the reaction mixture an equivalent amount of a tertiary amine, suchas triethylamine. Inthose instances it is assumed that a reactiveintermediate of the formula R,CO-N=CH-'-CCl is formed, which then reactsfurther to undergo an addition reaction with the diamine Ill and forms acompound of the formula I. 5 The end products of the formula I obtainedin this manner are weak bases; some of them are colorless crystallinesolids which are sparsely soluble in water, while others are oily orglassy-amorphous substances which may be purified by way of theirhydrohalic acid addition salts. However, all of the bases are relativelyeasily soluble in dimethylsulfoxide, tetrahydrofuran, cyclohexanonc,dimethylformamidc, N-methyl-pyrrolidone and butyrolactonc.

The starting compounds of the formula ll may be prepared pursuant toknown processes, such as by exchange of the hydroxyl group in a compoundof the formula R,CO-NHCHOHCCI for a substituent X, as defined inconnection with formula II above.

The following examples further illustrate the present invention and willenable others skilled in the art to understand it more completely. Itshould be understood, however, that the invention is not limited solelyto the particular examples given below.

EXAMPLE 1 N,N'-Bis-phenyl-N,N'-bis-[( l-formamido-2,2,2- trichloro)-ethyll-ethylenediamine.

A mixture consisting of 0.04 mol of N,N-bis-phenylethylenediamine, 8.3gm (0.08 mol +3 percent) of triethyl-amine and 50 cc of drytetrahydrofuran was added dropwise over a period of 1 hour to a solutionof 16.9 gm (0.08 mol) of N-[(l,2,2,2-tetrachloro)-ethyl]- formamide in80 cc of dry tetrahydrofuran, accompanied by stirring. Thereafter, thereaction mixture was stirred at room temperature for one hour more, theprecipitated triethylamine hydrochloride was separated by vacuumfiltration, and the filtrate was evaporated in vacuo at 4050 C. The oilyresidue crystallized upon being digested with ether, yielding 74 percentof theory of N,N'-bis-phenyl-N,N -bis-[( l-formamido-2,2,2-trichloro)-ethyll-ethylenediamine, m. p. l68-l70 C (decomp.), of theformula 45 EXAMPLE 2 Using a procedure analogous to that described inEx- 3 was prepared from N-[(l,2,2,2 tetrachloro)-ethyl]- pivalyl-amineand l,2-dianilino-ethane. The yield was 55 percent of theory.

EXAMPLE 3 Using a procedure analogous to that described in Example 1,N,N'-bis-phenyl-N,N '-bis-[( 1- trichlcroacetamido-Z,2,2-trichloro)ethyl]- I ethylenediamine, m.p. l76-180 C. (decomp.), of the formula wasprepared from N-[(l,2,2,2-tetrachloro)-ethyl]- trichloro-acetamide and1,2-dianilino-ethane. The yield was 33 percent of theory.

EXAMPLE 4 Using a procedure analogous to that described in Example l,N,N'-bis-benzyl-N,N-bis-[( l-formamido-2,2,Z-trichloro)-ethyll-ethylenediamine, an amorphous substance, m. p.about 50 C., of the formula was prepared from N-[( l,2,2,2-tetrachloro)-ethyl]-formamide andN,N'-bis-benzyl-ethylenediarnine. The yield was 90 percent of theory.

EXAMPLE 5 EXAMPLE 6 Using a procedure analogous to that described inExample l, N-benzyl-N,N'-bis-[(l-formamido-2,2,2- trichloro)-ethyl]- l,3-propylenediamine, an amorphous substance, was prepared from N-[( l,2,2,2- tetrachloro)-ethyl]-formamide and N-benzyl-l,3-propylenediamine. The yield was 90 percent of theory.

EXAMPLE 7 Using a procedure analogous to that described in Example l,N-benzyl-N,N '-bis-{( 1 -formamido-2,2,2-trichloro)-ethyl]-ethylenediamine, an amorphous sub- 4 stance, wasprepared from N-[(l,2,2,2 tetrachloro)' ethyl1-formamideandN-benzyl-ethylenediamine. The yield was 92 percent of theory.

EXAMPLE 8 Using a procedure analogous to that described in Example l,N,N'-bis-(p-chloro-phenyl)-N,N'-bis-[(1-formamido-2,2,2-trichlor'o)-ethyll-methylenediamine, m. p. l74-l78 C. (decomp.), ofthe formula J's-Cy).

was prepared from N-[( 1,2,2,2tetrachloro)-ethyl] tormamide andbis-(p-chloro-anilino )-methane. The yield was 15 percent of theory.

EXAMPLE 9 Using a procedure analogous to that described in Example l,N,N '-bis-( 3 ,4-dichloro-phenyl)-N,N -bis[( 1- form amide-2,2,Z-trichloro )-ethyl l-methylenediamine m. p. l98-202 C. (decomp.), wasprepared from N- l,2,2,2-tetracl1loro)-ethyl]-formamide and bis-(3,4-dichloro-anilino)-methane. The yield was 21 percent of theory.

EXAMPLE 10 Using a procedure analogous to that described in Example l,N,N '-bis-phenyl-N ,N '-bis-[( l-formamido-2,2,2-trichloro)-ethyl]-methylenediamine, m. p. I02l04 C. (decomp.), wasprepared from N- l,2,2,2-tetrachloro)-ethyl]-formamide andhisanilino-methane. The yield was 20 percent of theory.

EXAMPLE 11 Using a procedure analogous to that described in Example lN,N '-bis-phenyl-N ,N '-bis-[( ltrime thylacetamido-2,2 ,Z-trichloro)-ethyl 1- methylenediamine, m. p. l26-l 29 C. (decomp.), was preparedfrom N-[( 1,2,2 ,2-tetrachloro ethyl trime'thylacetamide andbis-anilino-methane. The yield was 33 percent of theory.

EXAMPLE 12 Using a procedure analogous to that described in Example lN-(p-chloro-benzyl)-N,N '-bis-](1-formamido-2,2,Z-trichloro)ethyl1-ethylenediamine, an amorphoussubstance, was prepared from N-[( l, 2,2,2-tetrachloro)-ethyl]-formamide and N-(p-chlorobenzyl)-ethylenediamine.The yield was 89 percent of theory.-

EXAMPLE 13 Using a procedure analogous to that described in Example l,N-(2-chloro-benzyl)-N,N'-bis-[(1-formamido-2,2,2-trichloro)-ethyll-ethylenediamine,an amorphous substance, was prepared from N-[( 1 ,2,2,2-tetrachloro)-ethyl]-formamide and N-(2-chloro benzyl)-ethylenediamine.The yield was 70 percent of theory.

EXAMPLE 14 Using a procedure analogous to that described in Example l,N-(3,4-dichloro-benzyl)-N,N'-bis-[(1-formamido-2,2,2-trichloro)-ethyl]ethylenediamine,an amorphous substance, was prepared from N-[( 1 ,2,2,2-tetrachloro)-ethyl]-formamide andN-(3,4-dichlorobenzyl)-ethylenediamine. The yield was 75 percent oftheory.

EXAMPLE 15 EXAMPLE l6 Using a procedure analogous to that described inExample l, N,N'-bis-phenyl-N,N-bis-[(l-acetamido-2,2,2-trichloro)-ethyl]-ethylenediamine, m. p. 208-21 0 C.(recrystallized from isopropanol), of the formula was prepared fromN-[(l,2,2,2-tetrachloro)-ethyl]- acetamide andN,N-bis-phenyl-ethylenediamine.

EXAMPLE 17 l CH2 stance which began to melt at 60 was prepared fromN-[(l,2,2,2-tetrachloro)-ethyl]- acetamide andN,N'-bis-(2,4-dibromo-phenyl)- ethylenediamine.

EXAMPLE 18 Using a procedure analogous to that described in Example l,N,N'-bis-(p-bromo-phenyl)-N,N'-bis-[(1-acetamido-2,2,2-trichloro)-ethyl]ethylenediamine, m.

p. 202-203 C. (recrystallized from ethanol), of the formula 0 HaCNH-CHCCIQ was prepared from acetamide and cthylenediaminc.

EXAMPLE 19 Using a procedure analogous to that described in Example l,N-phenyl-N,N'-bis-[(l-formamido-2,2,2-trichloro)-ethyl]-ethylenediamine, an amorphous sub- C., ofthe formulawas prepared from N-[( l ,2,2,Z-tetrachloro)-ethyl]-formamide andN-phenyl-ethylenediamine.

The compounds according to the present invention, that is, thoseembraced by formula 1 above, have useful properties. More particularly,the compounds of the invention are highly effective fungicides with verylow phytotoxicity; thus they may be effectively used for prophylactic aswell as curative treatment of plants against phytopathogenic fungi. Forinstance, complete prevention against infestation is achieved in thecase of a number of true mildew fungi, such as Erysiphe graminis andErysiphe polygoni. Furthermore, the compounds according to the inventionare effective in combatting rust fungi, such as Uromycesfabae andPuccinia arenariae; causes of wilting diseases, such as Verticilliumalboatrum; causes of plant scabs, such as Venturia inaequalis; moldfungi, such as Aspergillus niger; and various other harmful fungi, suchas Fusaria and Ophiobuli.

Particularly noteworthy is the good systemic effect of the novelcompounds.

The compounds according to the presentinvention The compounds of theformula I also exhibit very low toxicity toward warm-blooded animals.

For prophylactic or curative treatment of plants against fungusinfestation, the compounds according to the present invention areincorporated as active ingredients into customary fungicidalcomposition, i.e. compositions consisting essentially of a liquid orcomminuted solid inert carrier and an effective fungicidal amount of theactive ingredient, such as .solutions, emulsion concentrates,suspendable or wettable powders, dusting powders, granulates and sprays.The active ingredient content of these compositions is about 0.5 to 85percent by weight, preferably 0.5 to 50 percent by weight.

For instance, an emulsion concentrate contains about 0.5 to 20 percentby weight, preferably to 10 percent by weight, of a compound of theFormula l. Suitable solvents for the preparation of emulsionconcentrates comprising a compound of the invention as an activeingredient are, for example, mixtures of dimethylformamide' orN-methylpyrrolidone with alcohols or glycols. Suitable emulsifiers andwetting agents which may be used for the preparation of such emulsionconcentrates are non-ionic compounds, such as nonyl-phenol polyglycolether, or mixtures of nonionic and ionic, preferably anionic, compoundsas well as ampholytes. The emulsifier content of the emulsionconcentrate is about 0.5 to 45 percent by weight, preferably 5 to 25percent by weight.

The active ingredient content of a wettable powder is about 0.5 to 80percent by weight, preferably 5 to 25 percent by weight. Suitableemulsifiers and wetting agents which may be used for the preparation ofwettable powders are non-ionic or ionic compounds of the type describedin the preceding paragraph; the total amount of emulsifier and wettingagent in such wettable powders is about 0.5 to 25 percent by weight,preferably 2 to 25 percent by weight. Suitable powdery inert carriersare, for example, bentonite, kaolin and colloidal silicic acid.

The fungicidal compositions comprising a compound of the presentinvention as an active ingredient are, if necessary, diluted with waterto an active ingredient concentration of 0.5 to 0.00001 percent prior totheir use for combatting fungi. Dusting powders may have a higher activeingredient concentration. The upper limit for the applicationconcentration is predicated upon the relatively low phytotoxicity.

The following examples illustrate a few fungicidal compositionscomprising a compound of the instant invention as an active ingredientand represent the best mode contemplated of putting the invention topractical use. The percentages are percent by weight.

EXAMPLE 2O Dusting Powder Compound of Example 1 1% Talcum 98%Methylcellulose 1% EXAMPLE 21 Wettable Powder Compound of Example 2 25%Kaolin Colloidal silicic acid 10% Lignin sulfonate (dispersing agent) 9%Sodium tetrapropylene benzene sulfonate (wetting agent) 1% Thecomponents are admixed, the mixture is milled until homogeneous, andprior to use the powder is suspended in an amount of water such that theactive ingredient concentration in the aqueous suspension is from0.00001 to 0.5 percent by weight.

EXAMPLE 22 Emulsion Concentrate Compound of Example 3 10% Sodiumtetrapropylene benzene sulfonate (anionic emulsifier) 5% Nonylphenolpolyglycol ether (non-ionic emulsifier) 20% Propyleneglycol 32.5%N-Methylpyrrolidone 32.5%

The components are uniformly admixed with each other, and prior to usethe resulting concentrate is diluted with water to the desired activeingredient content between 0.00001 and 0.5 percent by weight.

EXAMPLE 2 3 Aerosol Spray Compound of Example 4 0.05% Sesame oil 0.10%N-Methylpyrrolidone 10.00% Propellant gas 89.85%

The components are admixed in customary fashion, and the mixture ischarged into aerosol containers pro.- vided with a spray valve.

While the present invention has been illustrated with the aid of certainspecific embodiments thereof, it will be readily apparent to othersskilled in the art that the invention is not limited to these particularembodiments, and that various changes and modifications may be madewithout departing from the spirit of the invention.

We claim:

1. A compound of the formula wherein R is hydrogen, alkyl of one to fourcarbon atoms or trichloromethyl,

R is phenyl, benzyl, chlorophenyl, dichlorophenyl, chlorobenzyl,dichlorobenzyl, bromophenyl or dibromophenyl,

R is hydrogen, phenyl, benzyl or dichlorophenyl,

bromophenyl or dibromophenyl, and

n is l, 2 or 3.

2. A compound according to claim 1, which is N,N'- bis-phenyl-N,N-bis-[(1-formamido-2,2,2-trichloro)- ethyl]-ethylenediamine.

3. A compound according to claim 1, which is N,N- bis-phenyl-N,N-bis-[(l-pivaloylamino-2,2,2- trichloro)-ethyl]-cthylenediamine.

4. A compound according to claim 1, which is N,N'- bis-phenyl-N ,N'-bis-[(1-trichloroacetamido-2,2,2- trichloro)-ethyl]-ethylenediamine.

5. A compound according to claim 1, which is N,N'- bis-benzyl-N ,N'-bis-[( l-formamido-2,2,2-trichloro)- ethyl]-ethylenediamine.

6. A compound according to claim 1, which is N,N'-bis-benzyl-N,N'-bis-[(1-formamid0-2,2,2-trichloro)- ethyl]-l,3-propylenediamine.

7. A compound according to claim 1, which is N- benzyl-N ,N '-bis-[( 1-form amido-2,2,2-trichloro)- ethyl]-l ,3-propylencdiamine.

8. A compound according to claim 1, which benzyl-N,N'-bis-[(1-formamido-2,2,2-trichloro)- ethyl]-ethylenediamine.

9. A compound according to claim 1, which is N,N'-bis-(p-chloro-phenyl)-N,N '-bis-[(1-formamido-2,2,2-trichloro)-ethyl]-methylenediamine.

10. A compound according to claim 1, which isN,N'-bis-(3,4-dichlorophenyl)-N,N'-bis[(l-formamido-2,2,2-trichloro)-ethyl]-methylenediamine.

11. A compound according to claim 1, which is N,N'-bis-phenyl-N,N-bis[(l-formamido-2,2,2- trichloro)-ethyl]-methylenediamine.

12. A compound according to claim 1, which is is N- ,N-bis-phenyi-N,N'-bis-[( l-trimethylacetamido- 2,2,2-trichloro)-ethyl]-methylenediamine.

13. A compound according to claim 1, which is N-(pchloro-benzyl)-N,N'-bis-[( l -formamido-2,2,2-trichloro)-ethyl]-ethylenediamine.

14. A compound according to claim 1, which is N-( 2-chloro-benzyl)-N,N'-bis-[( l -formamido-2,2,2-trichloro)-ethyl]-ethylenediamine.

15. A compound according to claim 1, which is N- (3,4-dichloro-benzyl)-N,N-bis[( l-formamido-2,2,2-trichloro)-ethyl]-ethylenediamine.

16. A compound according to claim 1, which is N-(2,4-dichloro-benzyl)-N,N'-bis-[(1-formamido-2,2,2-trich1oro)-ethyl]-ethylenediamine.

17. A compound according to claim 1, which is N,N'-bis-phenyl-N,N-bis[(1-acetamido-2,2,2- trichloro)-ethyll-ethylenediamine.

18. A compound according to claim 1, which isN,N-bis-(2,4-dibromo-phenyl)-N,N-bis-[( 1-acetamido-Z,2,2-trichloro)-ethyl]-ethylenediamine.

19. A compound according to claim 1, which isN,N'-bis-(p-bromo-phenyl)-N,N'-bis-[( 1 -acetamido-2,2,2-trichloro)-ethyll-ethylenediamine.

20. A compound according to claim 1, which is N- phenyl-N,N '-bis-[(l-formamido-2,2,2-trichloro ethyl l-ethylenediaminc.

1. A compound of the formula
 2. A compound according to claim 1, whichis N,N''-bis-phenyl-N,N''-bis-((1-formamido-2,2,2-trichloro)-ethyl)-ethylenediamine.
 3. Acompound according to claim 1, which is N,N''-bis-phenyl-N,N''-bis-((1-pivaloylamino-2,2,2-trichloro)-ethyl)-ethylenediamine.
 4. Acompound according to claim 1, which is N,N''-bis-phenyl-N,N''-bis-((1-trichloroacetamido-2,2,2-trichloro)-ethyl)-ethylenediamine.5. A compound according to claim 1, which is N,N''-bis-benzyl-N,N''-bis-((1-formamido-2,2,2-trichloro)-ethyl)-ethylenediamine.
 6. Acompound according to claim 1, which is N,N''-bis-benzyl-N,N''-bis-((1-formamido-2,2,2-trichloro)-ethyl)-1,3-propylenediamine.
 7. Acompound according to claim 1, which isN-benzyl-N,N''-bis-((1-formamido-2,2,2-trichloro)-ethyl)-1,3-propylenediamine.
 8. A compound according to claim 1, which isN-benzyl-N,N''-bis-((1-formamido-2,2,2-trichloro)-ethyl)-ethylenediamine.9. A compound according to claim 1, which isN,N''-bis-(p-chloro-phenyl)-N,N''-bis-((1-formamido-2,2,2-trichloro)-ethyl)-methylenediamine.
 10. A compound according to claim 1, which isN,N''-bis-(3,4-dichlorophenyl)-N,N''-bis((1-formamido-2,2,2-trichloro)-ethyl)-methylenediamine.
 11. A compound according to claim 1, which isN,N''-bis-phenyl-N,N''-bis((1-formamido-2,2,2-trichloro)-ethyl)-methylenediamine.
 12. Acompound according to claim 1, which is N,N''-bis-phenyl-N,N''-bis-((1-trimethylacetamido-2,2,2-trichloro)-ethyl)-methylenediamine.13. A compound according to claim 1, which isN-(p-chloro-benzyl)-N,N''-bis-((1-formamido-2,2,2-trichloro)-ethyl)-ethylenediamine.
 14. A compound according to claim 1, which isN-(2-chloro-benzyl)-N,N''-bis-((1-formamido-2,2,2-trichloro)-ethyl)-ethylenediamine.
 15. A compound according to claim 1, which isN-(3,4-dichloro-benzyl)-N,N''-bis((1-formamido-2,2,2-trichloro)-ethyl)-ethylenediamine.
 16. A compound according to claim 1, which isN-(2,4-dichloro-benzyl)-N,N''-bis-((1-formamido-2,2,2-trichloro)-ethyl)-ethylenediamine.
 17. A compound according to claim 1, which isN,N''-bis-phenyl-N,N''-bis((1-acetamido-2,2,2-trichloro)-ethyl)-ethylenediamine.
 18. Acompound according to claim 1, which isN,N''-bis-(2,4-dibromo-phenyl)-N,N''-bis-((1-acetamido-2,2,2-trichloro)-ethyl)-ethylenediamine.19. A compound according to claim 1, which isN,N''-bis-(p-bromo-phenyl)-N,N''-bis-((1-acetamido-2,2,2-trichloro)-ethyl)-ethylenediamine.